Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Andrew J. Smith, Allan Young, Simon Rohrbach, Erin F. O'Connor, Mark Allison, Hong-Shuang Wang, Darren L. Poole, Tell Tuttle, John A. Murphy

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Abstract

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.
Original languageEnglish
Pages (from-to)13747–13751
Number of pages5
JournalAngewandte Chemie International Edition
Volume56
Issue number44
Early online date11 Sep 2017
DOIs
Publication statusPublished - 23 Oct 2017

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Keywords

  • electron-transfer reactions
  • hydride-transfer pathways
  • single-electron transfer
  • hydride delivery reactions

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